A polymer electrolyte fuel cell is a fuel cell in the form in which a polymer solid electrolyte is sandwiched between an anode and a cathode, a fuel is supplied to the anode, and oxygen or air is supplied to the cathode, whereby oxygen is reduced at the cathode to produce electricity. As the fuel, hydrogen, methanol, or the like is mainly used.
To enhance a reaction rate in a fuel cell and to enhance the energy conversion efficiency of the fuel cell, a layer containing a catalyst (hereinafter also referred to as a “fuel cell catalyst layer”) has been conventionally disposed on the surface of a cathode (air electrode) or the surface of an anode (fuel electrode) of the fuel cell.
As such a catalyst, noble metals have been generally used, and, among the noble metals, a noble metal stable at a high potential and having a high activity, such as platinum or palladium, has been mainly used. However, since these noble metals are expensive and limited in resource amount, development of substitutable catalysts has been desired.
Further, there has been a problem that the noble metals used on the surface of a cathode may be dissolved under an acidic atmosphere and are not suitable for uses requiring long-term durability. Accordingly, it has been strongly demanded that catalysts are developed which are not corroded under an acidic atmosphere and have excellent durability and high oxygen reducing ability.
As a catalyst substituted for noble metals, those entirely free of noble metals, such as base metal carbides, base metal oxides, base metal carbonitroxides, chalcogen compounds, and carbon catalysts, have been reported (for example, see Patent Literature 1 to Patent Literature 4). These materials are inexpensive and abundant in resource amounts as compared with noble metal materials such as platinum.
However, these catalysts containing base metal materials described in Patent Literature 1 and Patent Literature 2 have a problem that practically sufficient oxygen reducing ability is not obtained.
Further, the catalysts described in Patent Literature 3 and Patent Literature 4, although exhibiting high oxygen reduction catalytic activity, have a problem that stability under fuel cell operating conditions is not sufficient.
As a catalyst substituted for noble metals, Nb and Ti carbonitroxides in Patent Literature 5 and Patent Literature 6 can effectively express the above-described performance and thus have received particular attention.
Although the catalysts described in Patent Literature 5 and Patent Literature 6 have extremely high performance as compared with conventional catalysts substituted for noble metals, a portion of the production step thereof needs to include heat treatment under a high temperature of 1600° C. to 1800° C. (for example, Example 1 of Patent Literature 5 or Example 1 of Patent Literature 6).
Such high-temperature heat treatment is not industrially impossible but involves difficulty and causes increase in equipment cost and difficulty in operation control, leading to increase in production cost, and, thus, the development of a method capable of inexpensive production has been desired.
Patent Literature 7 reports a technology relating to the production of a carbon-containing titanium oxynitride that contains carbon, nitrogen, and oxygen.
However, according to the production method described in Patent Literature 7, the production of the carbon-containing titanium oxynitride requires two-stage synthesis: the production of a titanium oxynitride by reacting a nitrogen-containing organic compound with a titanium precursor; and the production of a carbon-containing titanium oxynitride by reacting a phenol resin with the titanium oxynitride precursor, and thus involves complicated steps. In particular, the production of the titanium oxynitride precursor requires complicated steps including stirring, heating, and refluxing at 80° C. as well as cooling and concentrating under reduced pressure, thus resulting in high production cost.
Further, since the phenol resin is a thermosetting resin having a three-dimensional network structure, it is difficult to homogenously mix and react the phenol resin with a metal oxide. In particular, there is a problem that since the thermal decomposition temperature of the phenol resin is 400° C. to 900° C., a carbonization reaction due to the complete decomposition of the phenol resin is unlikely to take place at a temperature of 1000° C. or less.
Furthermore, Patent Literature 7 and Non-Patent Literature 1 only describe applications to a thin film for a solar collector and a photocatalyst as uses thereof, failing to disclose or examine a method for producing a metal carbonitroxide having particulate or fibrous shape or the like that is highly useful as an electrode catalyst and uses thereof.
Patent Literature 8 discloses a method for producing an electrode catalyst characterized by burning a mixed material of an oxide and a carbon material precursor but an electrode catalyst having sufficient catalytic performance has not been obtained.
Further, Patent Literature 9 discloses a fuel cell electrode catalyst prepared by using a polynuclear complex of cobalt and the like but this catalyst has had problems that a cost is high and its catalytic activity is insufficient.
Non-Patent Literature 2 discloses a method for producing an electrode catalyst characterized by burning a mixed material of a titanium alkoxide and a carbon material precursor but the production step does not use an organic substance containing nitrogen and thus an electrode catalyst having sufficient catalytic performance has not been obtained.
Patent Literature 10 discloses a method for producing an electrode catalyst, comprising burning a metal compound, such as zirconium hydroxide, and a carbon material precursor, under a condition where the carbon material precursor can transit to a carbon material (e.g., 400 to 1100° C.) but an electrode catalyst having sufficient catalyst performance has not been obtained.
In addition, Patent Literature 11 discloses a method for producing a fuel cell electrode catalyst, comprising: a step 1 of mixing at least a compound containing a transition metal (element of group 4 or group 5 of the periodic table), a nitrogen-containing organic compound, and a solvent to obtain a catalyst precursor solution; a step 2 of removing the solvent from the catalyst precursor solution; and a step 3 of heat-treating a solid residue, obtained in the step 2, at comparatively low temperature, to obtain an electrode catalyst, but does not disclose a method for producing a fuel cell electrode catalyst, comprising a step of bringing an aqueous solution of a transition metal compound (1) into contact with ammonia and/or ammonia water to generate a precipitate containing an atom of the transition metal, as described below.